The present invention concerns a flavor delivery system which can be used to produce finished drinks and foods wherein the flavors are unexpectedly stabilized against flavor degradation and off note development.
1. Field of the Invention
The flavorants which are to be used in the flavor delivery system of the present invention include in particular edible, or essential, oils. While it is well known to extract these essential oils from plants and meat, they are generally sensitive to air and temperature, and have a short life. It has been difficult to preserve these oils as flavorants in stable form in end products such as fruit drinks where a considerable time may elapse between formulation and consumption of the end product. While the problem is often circumvented by resorting to stable artificial flavors and fragrances, there remains a consumer preference for natural flavors and fragrances.
Natural flavorant oils are generally provided In the form of emulsions. Emulsions, including microemulsions, are usually classified as oil and/or fat emulsified in water (O/W) or water emulsified In oil and/or fat
2. Description of the Related Art
For example, U.S. Pat. No. 5,320,863 entitled xe2x80x9cTransparent oil-in-water microemulsion flavor concentratexe2x80x9d (Chung et al) teaches a stable transparent oil-in-water microemulsion concentrate consisting essentially of:
(i) water; (ii) one or more hydrophobic flavor or fragrance oils; and (iii) one or more surfactants wherein the mixing ratio of the water, oil and surfactant is, within a specified range shown in FIG. 1A. Also described is a process for preparing such transparent microemulsion compositions, a mouthwash containing said transparent microemulsion compositions, a process for preparing same, and a perfume composition containing said transparent microemulsion compositions.
U.S. Pat. No. 4,835,002 entitled xe2x80x9cMicroemulsions of oil in water and alcoholxe2x80x9d (Wolf) teaches microemulsions of flavor oils in a matrix of water for use in certain products such as beverages. The microemulsions contain 25-80 wt. % alcohol (such as propylene glycol), 1-30 wt. % edible surfactant (such as Tween 60) and 1-25 wt. % essential oil, and the balance water to make 100 wt. %. The alcohol may be ethanol, propylene glycol, glycerin, sugar, sugar alcohol, and mixtures thereof. The microemulsions are indicated to be microbiologically and thermodynamically stable for long periods of time under ambient conditions of storage and use. However, water is an indispensable part of this microemulsion, and the ratio by weight of alcohol to surfactant is 8:1 to 20:1.
There remains a need for a more stable, non-aqueous flavor delivery system. Systems containing water are not desirable in some food products. To give a first example, microwave popcorn consists of a mix of corn, salt, oil and flavorings. It is not desirable to add flavors (usually needed at a high level in this product) that contain water to this product. To give a second example, in the manufacture of dry systems (such as beverage powders) the addition of flavors that contain water is not desirable.
Non-liquid forms of flavor delivery systems are known. U.S. Pat. No. 4,232,047 entitled xe2x80x9cFood supplement concentrate in a dense glasseous extrudatexe2x80x9d (Sair, et al.) teaches a food supplement concentrate of an ingestible agent such as a seasoning, flavoring, oleoresin, essential oil, vitamin, mineral, and mixtures thereof encapsulated, enveloped or otherwise encased as a dispersed microphase within but recoverable from a matrix of encapsulating medium such as a starch, protein, flour, modified starch, gum, and mixtures thereof. The glass-like, unexpanded extrudate is reported to be an excellent matrix for the incorporation of a mixture of lemon flavoring and citric acid. However, the product must be exposed to hot (boiling) water to release of the flavor.
U.S. Pat. No. 4,888,186 entitled xe2x80x9cMethod for producing flavored popcornxe2x80x9d (Cooley et al) teaches a fat-flavor system prepared by dry-blending solid particles of fat (preferably a partially hydrogenated vegetable oil such as cottonseed, soybean and mixtures thereof) with a flavoring. The fat has a melting point of no less than about 95xc2x0 F. so that the fat-flavor system comprises free-flowing particles at room temperature. The fat-flavor system is sprinkled onto hot, popped corn wherein the fat melts and the flavoring is adhered to the popcorn producing a flavored popcorn having an even flavor distribution and without a waxy-mouth feel. This system is not designed for delivering heat or oxidation sensitive ingredients such as citric acid, is not readily incorporated into a drink or food, and is not a liquid at room temperature.
It is also known to micro-encapsulate flavor oils: however, this method is complex and expensive In terms of requirements in skilled labor and materials.
U.S. Pat. No. 4,343,823 entitled xe2x80x9cLiquid seasoning compositions IVxe2x80x9d (Todd et al) teaches a homogeneous liquid condimental composition, useful in flavoring or coloring foods and beverages and which is dispersible in both oil and water, consisting essentially of (1) monoglyceride of caproic and/or caprylic and/or lauric acid, (2) polyglycerol ester of at least one fatty acid, and (3) one or more condiments selected from edible flavorings and edible colorings, the ratio by weight of (1) plus (2) to (3) being at least 1:4, preferably at least 1:3, especially about 1:1, the condiment portion (3) preferably comprising at least one condiment selected from the group consisting of (a) spice oleoresins, (b) essential oils, and (c) edible colorings, the ratios by weight of (2) to (1) preferably being between about 1:3 and 3:1, and the condiment portion (3) preferably comprising oleoresin black pepper.
Flavored oils are well known, but these are not what is referred to herein as a flavor delivery system. For example, U.S. Pat. No. 5,320,862 entitled xe2x80x9cEdible, multipurpose flavored oil substantially free of flavoring agent particlesxe2x80x9d (La Tona) teaches a method for preparing a pre-flavored oil substantially free of flavoring agent in a particulate form. In accordance with the method of this invention, a vegetable or nut oil is contacted with a garlic or onion flavoring agent in a particulate form at a temperature between 100xc2x0 C. and 200xc2x0 C. for 15 minutes to 90 minutes. After this heating period flavoring agent in particulate form is removed from the oil. This system thus provides a flavored cooking oil, not a concentrated flavor delivery system.
U.S. Pat. No. 5,607,715 entitled xe2x80x9cFlavored cooking oil having reduced room aromaxe2x80x9d (Beharry et al) disclosed flavored oils for use in deep frying, stir-frying and marinating, which when heated, exhibit reduced aroma. The flavored oils consist essentially of an edible oil (98.5%-99.94%), a flavoring agent (0.01% to 1%) and a polyoxyethylene sorbitan monoester such as Tween 80 (0.05 to 0.5%) incorporated in the edible oil but not the flavoring. This composition would be referred to as a flavored cooking oil, not a concentrated flavor delivery system.
The present invention was made and based on the surprising discovery that an anhydrous flavor delivery system being liquid at a temperature of 30xc2x0 C. can be produced by combining
(a) 10-40% by weight of a flavoring composition,
(b) 20-50% by weight of a surfactant system consisting essentially of one or more surfactants,
(c) 20-50% by weight of an alcoholic composition, consisting essentially of one or more alcohols with two or more hydroxy groups per molecule, and, optionally,
(d) up to 10% by weight of at least one other additive typically used in flavor and/or food manufacturing,
wherein the total amount of ingredients (a), (b), and (c) is at least 90% by weight.
In the above definition, the term xe2x80x9csurfactant systemxe2x80x9d characterizes individual, or combinations of, surfactants, and the term xe2x80x9calcoholic compositionxe2x80x9d characterizes individual, or combinations of, (polyhydric) alcohols.
Although the term xe2x80x9cMicroemulsionxe2x80x9d might be a proper term for describing the flavor delivery system of the present invention, it is not used hereafter as it implies the presence of water. In the flavor delivery system of the present invention it is the alcoholic composition which constitutes the continuous or outer phase, and the flavoring composition constitutes the inner phase.
The anhydrous flavor delivery system according to the present invention is usually obtained by
(a) mixing corresponding amounts of said flavoring and said surfactant system (typically the flavoring ingredient is added to the surfactant),
(b) adding a corresponding amount of said alcoholic composition to the mixture obtained by step (a), and
(c) mixing the admixture obtained by step (b).
In comparison with the edible concentrated microemulsion disclosed In the U.S. Pat. No. 4,835,002 (Wolf) the flavor delivery system according to the present invention advantageously comprises no water, which is known to be, even in very small amounts, a catalyst for chemical reactions including hydrolysis and subsequent oxidation adversely effecting flavorants.
Furthermore, in comparison with the U.S. Pat. No. 4,835,002 (Wolf) the weight ratio of the alcoholic composition and the surfactant system is considerably lower in the flavor delivery system of the present invention. According to the present invention said alcoholic composition and said surfactant system are present in a weight ratio to each other in the range of 0.4-2.5, whereas according to the U.S. Pat. No. 4,835,002 the weight ratio of alcohol and surfactant is in the range of about 6-20. Surprisingly, it has been found that a self-stabilized flavor delivery system can be obtained in absence of water, when the flavor delivery system contains a large enough portion of said surfactant system.
Furthermore, again in comparison with the U.S. Pat. No. 4,835,002 (Wolf) it was surprisingly found that only alcohols with two or more hydroxy groups per molecule can be successfully used in producing an anhydrous flavor delivery system according to the present invention. Monovalent alcohols like ethanol can not be used successfully.
Advantageously, the anhydrous flavor delivery system according to the present invention tolerates high levels of acids, even incorporation of pure acids at high levels (see Example 8 below).
In the anhydrous flavor delivery system according to the present invention said surfactant and said flavoring composition are present in a weight ratio to each other of about 0.5-5.
Preferably, the anhydrous flavor delivery system according to the present invention comprises between 15 and 30% by weight of said flavoring composition. I.e. said surfactant system and said flavoring composition are present in a weight ratio to each other of preferably 0.66-3.33.
The main components of the anhydrous flavor delivery system according to the invention will now be individually discussed in greater detail.
Flavoring Composition:
The flavoring composition comprises one ore more flavorants selected from the following group:
(a) essential oils
(b) taste contributing alcohols comprising between three and sixteen carbon atoms per molecule and containing only one hydroxyl group per molecule,
(c) aldehydes comprising between three and sixteen carbon atoms per molecule,
(d) organic acids comprising between three and sixteen carbon atoms per molecule,
(e) organic esters comprising between three and sixteen carbon atoms per molecule,
(f) lactones of the general formula CxH2xxe2x88x922O2 comprising between five and eighteen carbon atoms per molecule, and
(g) ketones comprising between four and fourteen carbon atoms per molecule.
The essential oils mentioned as subgroup (a) above include flavoring aromatic compounds and/or oils, oleoresins and extracts derived from plants, leaves, flowers, fruits and so forth, and combinations thereof. These flavoring oils may be used individually or In a mixture as is well known in the art.
The edible, or essential, oils derived from plant matter are obtained from various parts of the plants from which they obtained, i.e., leaves, fruit, bark, root, grass, wood, heartwood, gum, balsam, berries, seed, flowers, twigs, and buds (Giovanni Fenaroli, xe2x80x9cHandbook of Flavor Ingredients,xe2x80x9d volume 1 (Natural), Volume 2 (Synthetic), CRC Press, 1971; S. Arctander, xe2x80x9cPerfumes and Flavor Chemicals,xe2x80x9d Montclair, N.J., 1969, 2 volumes).
The edible oils include all those natural edible oils normally extracted, as such, from their plant matter or animal source, usually, but not exclusively, by steam distillation, and without any dilution in a solvent or carrier. Artificial or synthetic forms of the natural edible oils may also be used.
These essential oils would include all those disclosed by S. Arctander and G. Fenaroli, supra, which are the more tasteful types of edible oils, and tend to be liquid at about 20-25xc2x0 C., and including those set forth in Table 1.
and other essential oils used in beverages and foods for flavors such as coffee, tea, cherry, apple, pineapple, and vanilla.
The useful oils would also include those which are relatively tasteless, or not normally used as essential oils for taste-imparting purposes. These less tasteful oils are, for the most part glyceride based, saturated or unsaturated, materials which are liquids, or pourable, at temperatures in the range of about 20xc2x0 to 75xc2x0 C., and are derived from plant or animal (warm- or cold-blooded) sources.
Such relatively tasteless oils derived from plant sources would include fruit, or vegetable or nut derived oils such as olive oil, corn oil, soyabean oil, sunflower seed oil, peanut oil, coconut oil, safflower oil, palm kernel oil, cocoa butter, palm oil, cottonseed oil, sesame seed oil, rapeseed oil, linseed oil, and castor oil.
Such relatively tasteless oils derived from warm blooded animal sources would include butter fat, lard (hogs) tallow (cattle and sheep), and whale oil, and those derived from cold blooded animal sources would include fish liver oils and sardine oils.
The oils may be used individually: or in mixtures of two or more thereof in the flavor delivery system of the present invention.
The flavorants prefered are those from the subgroups (a)-(g) which are liquid at room temperature. However, flavorant powders and the like (e.g. vanillin powder) can be integrated in the flavor delivery system according to the present invention in at least an amount which corresponds to their solubility in the admixture of the other components of the flavoring composition. Solid flavorants (powders) which have a very high solubility in the corresponding alcoholic composition of a flavor delivery system according to the present invention can even be included into said flavor delivery system in excess of their solubility in the other components of the flavoring phase.
Surfactant System:
The surfactant system, which is present in an amount of 20-50% by weight in the anhydrous flavor delivery system according to the present invention, preferably comprises one or more non-ionic-surfactants. As already mentioned above, the term xe2x80x9csurfactant systemxe2x80x9d characterizes Individual, or combinations of, (preferably non-ionic) surfactants.
The non-ionic surfactants used in the practice of invention can be selected from those well known in the art as non-ionic surfactants employed In the flavor and/or food industry.
Favorably, the composite hydrophilic/lipophlc balance (HLB) value of the surfactant system is between 6 and 18, preferably between 9 and 18.
Surfactants which have HLB values which are outside these ranges may be blended with each other and/or with surfactants having HLB values which are within such ranges, as long as the HLB value of the composite blended surfactant system has a HLB value within that of the desired ranges of values. The HLB value of such combinations of surfactants would be calculated or determined the same way as are the HLB values for the individual surfactants.
The HLB value concept of, and determination thereof for, surfactants is disclosed by Milton J. Rosen in xe2x80x9cSurfactants and Interfacial Phenomenaxe2x80x9d, J. Wiley and Sons, New York, N.Y., 1978, pages 242-245 or by Kirk-Othmer, Encyclopedia of Chemical Technology, 3rd Edition, Vol. 8, 1979, at pages 910-915.
The respective listings of HLB values by these authors may, in some cases, provide slightly different numerical HLB values, or ranges therof, for the same surfactants, due to differences in the respective measuring techniques used by such authors. Each of such respective ranges or values, however, is useful for the purposes of the present Invention.
Examples of suitable surfactants include the following:
TWEEN(copyright) 20 (Polyoxyethylene (20) Sorbitan Monolaurate) (TWEEN(copyright) is a Trademark of ICI Americans of Wilmington, Del.);
TWEEN(copyright) 40 (Polyoxyethylene (20) Sorbitan Monopalmitate);
TWEEN(copyright) 60 (Polyoxyethylene (20) Sorbitan Monostearate);
CREMOPHOR(copyright) RH 40 (Ethoxy Hydrogenated Castor Oil) (CREMOPHOR(copyright) is a Trademark of BASF Aktiengesellschaft of D-6700 Ludwigshafen, Federal Republic of Germany);
CREMOPHOR(copyright) RH 60 (Ethoxy Hydrogenated Castor Oil);
GENAPOL(copyright) (Alcohol Polyglycol Ether) (GENAPOL(copyright) is a trademark of Hoechst Aktiengesellschaft of D-6230 Frankfurt AM Main No. 90, Postfach 80, Federal Republic of Germany);
TRYCOL brand surfactants available from Henkel Corp./Emery Group, Ohio.
TERGITOL surfactents made by Union Carbide Corp., Conn.
Further suitable surfactants are given in the Examples below.
Nonionic surfactants are typically compounds-produced by the condensation of alkylene oxide groups (hydrophilic in nature) with an organic hydrophobic compound, which can be aliphatic or alkyl-aromatic in nature, but can include other surfactants that do not possess a charge group. The length of the hydrophilic or polyoxyalkylene radical which is condensed with any particular hydrophobic group can be readily adjusted to yield a water-soluble compound having the desired degree of balance between hydrophlic and hydrophobic elements.
For example, surfactants can be formed by condensing ethylene oxide with a hydrophobic base formed by the condensation of propylene oxide with propylene glycol. The hydrophobic portion of the molecule which, of course, exhibits water insolubility has a molecular weight of from about 1,500 to about 1,800. The addition of polyoxyethylene radicals to this hydrophobic portion tends to increase the water solubility of the molecule as a whole and the liquid character of the products is retained up to the point where polyoxyethylene content is about 50% of the total weight of the condensation product.
Examples of classes of nonionic surfactants are:
Alkyl phenol ethoxylates. The polyethylene oxide condensates of alkyl phenols, e.g., the condensation products of alkyl phenols having an alkyl group containing from about 6 to 12 carbon atoms in either a straight chain or branched chain configuration, with ethylene oxide, the said ethylene oxide being present in amounts equal to 10 to 60 moles of ethylene oxide per mole of alkyl phenol. The alkyl substituent in such compounds can be derived from polymerized propylene, diisobutylene, octane, or nonane, for example.
Polyethylene gycol/polypropylene glycol block copolymers. Those derived from the condensation of ethylene oxide with the product resulting from the reaction of propylene oxide and ethylene diamine products which can be varied in composition depending upon the balance between the hydrophobic and hydrophilic elements which is desired. For example, compounds containing from about 40% to about 80% polyoxyethylene by weight and having a molecular weight of from about 5,000 to about 11,000 resulting from the reaction of ethylene oxide groups with a hydrophobic base constituted of the reaction product of ethylene diamine and excess propylene oxide, said base having a molecular weight of the order of 2,500 to 3,000, are satisfactory.
Fatty alcohol and fatty acid ethoxylates. The condensation product of aliphatic alcohols having from 8 to 18 carbon atoms, in either straight chain or branched chain configuration with ethylene oxide, e.g., a coconut alcohol ethylene oxide condensate having from 10 to 30 moles of ethylene oxide per mole of coconut alcohol, the coconut alcohol fraction having from 10 to 14 carbon atoms. Other ethylene oxide condensation products are ethoxylated fatty acid esters of polyhydric alcohols (e.g., Tween 20-polyoxyethylens (20) sorbitan monolaurate).
Long chain tertiary amine oxides. Long chain tertiary amine oxides corresponding to the following general formula:
R1R2R3Nxe2x86x92O
wherein R1 contains an alkyl, alkenyl or monohydroxy alkyl radical of from about 8 to about 18 carbon atoms, from about 0 to about 10 ethylene oxide moieties, and from 0 to 1 glycerol moiety, and R2 and R3 contain from 1 to about 3 carbon atoms and from 0 to about 1 hydroxy group, e.g., methyl, ethyl, propyl, hydroxy ethyl, or hydroxy propyl radicals. The arrow in the formula is a conventional representation of a semipolar bond. Examples of amine oxides suitable for use in this invention include dimethyldodecylamine oxide, oleyldi(2-hydroxy ethyl) amine oxide, dimethyloctylamine oxide, dimethyldecy-lamine oxide, dimethyltetradecylamine oxide, 3,6,9-trioxaheptadecyldiethylamine oxide, di(2-hydroxyethyl)-tetradecylamine oxide, 2-dodecoxyethyldimethylamine oxide, 3-dodecoxy-2-hydroxypropyldi(3-hydroxypropyl) amine oxide, dimethylhexadecylamine oxide.
Alkyl polvsaccharide (APS) surfactants such as the alkyl polglycosides. Such surfactants are APS surfactants having a hydrophobic group with about 6 to about 30 carbon atoms and polysaccharide (e.g., polyglycoside) as the hydrophilic group. Optionally, there can be a polyalkylene-oxide group joining the hydrophobic and hydrophilic moieties. The alkyl group (i.e., the hydrophobic moiety) can be saturated or unsaturated, branched or unbranched, and unsubstituted or substituted (e.g., with hydroxy or cyclic rings).
Polyethyle glycol (PEG) glycerol fatty esters, such as those of the formula R(O)OCH2CH(OH)CH2(OCH2CH2)nOH wherein n is from about 5 to about 200, preferably from about 20 to about 100, and R is an aliphatic hydrocarbyl having from about 8 to about 20 carbon atoms.
Alcoholic Composition:
The alcoholic composition consisting essentially of one or more alcohols with two or more hydroxy groups per molecule present in the anhydrous flavor delivery system according to the present invention preferably comprises at least one polyhydric alcohol with between three and eight carbon atoms per molecule. As already mentioned above, the term xe2x80x9calcoholic compositionxe2x80x9d characterizes individual, or combinations of, alcohols.
The most prefered polyhydric alcohols are those with three, four, five or six carbon atoms per molecule.
Propylene glycol, butylene glycol and hexylene glycol are the most prefered alcohols and can be used alone and/or in mixture with other alcohols possessing two or more hydroxy groups per molecule.
Other prefered alcohols are glycerol and sorbitol.
In anhydrous flavor delivery systems according to the present invention very often the flavoring composition and the alcoholic composition have a very low solubility in each other. In these cases, when the flavoring and the alcoholic composition are mixed in a weight ratio to each other of 0.2-2.0, in absence of the surfactant system a two-phase-system is obtained.
Other Additive:
As already mentioned, the anhydrous flavor delivery system of the present invention may contain, on an optional basis, up to 10% by weight of at least one other additive typically used in flavor and/or food manufacturing. In particular, the following food grade additives can be used:
preservatives, colorants, salt, intense sweeteners (natural and artificial).
The flavor delivery system according to the invention can be used to produce a beverage or food product which is unexpectedly flavor stabilized. In beverages, the flavor delivery system is remarkably stable as compared to conventional systems at lower pH-values. E.g., when the flavor composition contains citrus oils and the flavor delivery system is added to a beverage containing an acidulant such as citric acid, the rate of degredation (i.e the rate of development of off-notes) is decreased in comparison with control samples.
The following examples are merely illustrative of the present invention are not intended as a limitation upon the scope thereof.
In each of the following examples 1-20 for preparation of the flavor delivery system the surfactant(s) constituting the surfactant system are warmed to liquefy them, if necessary, and then the flavoring ingredient(s) constituting the flavoring composition are added. These are gently mixed for about ten minutes to ensure an adequate mixing.
The alcoholic composition consisting essentially of polyhydric alcohol(s), was then added and the resulting mixture mixed for an additional ten minutes. The resulting system is a clear liquid. The system may gel when refrigerated, but the gel will liquefy without any mixing when brought back to room temperature.
For each example, the percentage of each ingredient refers to the percentage of the material added by weight.
For each example, three substances are listed, the first substance being a typical flavorant, the second substance being a typical surfactant, and the third substance being a typical polyhydric alcohol for use in the flavor delivery system of the present invention.
The titles assigned to the examples are not meant to imply that the examples give recipes of commercially relevant flavor delivery systems, They primarily serve to demonstrate the capacity of the flavor delivery systems to incorporate the various chemical classes. For commercial products, the use of single flavor ingredients would not be typical. Further flavoring ingredients typical for the respective flavor can be added along with the flavorant stated in the respective example.